CN111362936A - Compound with olefinic bond-containing seven-membered ring as core and application thereof - Google Patents
Compound with olefinic bond-containing seven-membered ring as core and application thereof Download PDFInfo
- Publication number
- CN111362936A CN111362936A CN201811593762.1A CN201811593762A CN111362936A CN 111362936 A CN111362936 A CN 111362936A CN 201811593762 A CN201811593762 A CN 201811593762A CN 111362936 A CN111362936 A CN 111362936A
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- group
- represented
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- -1 dibenzofuranyl group Chemical group 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 10
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 10
- 241000720974 Protium Species 0.000 claims description 10
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 229910052722 tritium Inorganic materials 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000005549 heteroarylene group Chemical group 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000006836 terphenylene group Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 65
- 239000007858 starting material Substances 0.000 description 32
- 238000012360 testing method Methods 0.000 description 20
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 17
- 238000000921 elemental analysis Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000005525 hole transport Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000008204 material by function Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 2
- VUEGYUOUAAVYAS-JGGQBBKZSA-N (6ar,9s,10ar)-9-(dimethylsulfamoylamino)-7-methyl-6,6a,8,9,10,10a-hexahydro-4h-indolo[4,3-fg]quinoline Chemical compound C1=CC([C@H]2C[C@@H](CN(C)[C@@H]2C2)NS(=O)(=O)N(C)C)=C3C2=CNC3=C1 VUEGYUOUAAVYAS-JGGQBBKZSA-N 0.000 description 2
- MHSLDASSAFCCDO-UHFFFAOYSA-N 1-(5-tert-butyl-2-methylpyrazol-3-yl)-3-(4-pyridin-4-yloxyphenyl)urea Chemical compound CN1N=C(C(C)(C)C)C=C1NC(=O)NC(C=C1)=CC=C1OC1=CC=NC=C1 MHSLDASSAFCCDO-UHFFFAOYSA-N 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 2
- VKLKXFOZNHEBSW-UHFFFAOYSA-N 5-[[3-[(4-morpholin-4-ylbenzoyl)amino]phenyl]methoxy]pyridine-3-carboxamide Chemical compound O1CCN(CC1)C1=CC=C(C(=O)NC=2C=C(COC=3C=NC=C(C(=O)N)C=3)C=CC=2)C=C1 VKLKXFOZNHEBSW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940126540 compound 41 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 101100072645 Arabidopsis thaliana IPS3 gene Proteins 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001616 biphenylenes Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
- C07D491/14—Ortho-condensed systems
- C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/056—Ortho-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a compound taking an ethylenic bond-containing seven-membered ring as a core and application thereof, wherein the structure of the compound taking the ethylenic bond-containing seven-membered ring as the core is shown as a general formula (1). The compound provided by the invention has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
Description
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a compound taking an ethylenic bond-containing seven-membered ring as a core, a preparation method thereof and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved. Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transmission material, a light emitting material, an electron transmission material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant of the present invention provides a compound with an ethylenic bond-containing seven-membered ring as a core and an application thereof. The compound takes an ethylenic bond-containing seven-membered ring as a core, has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and higher Eg, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through structural optimization of the device.
The technical scheme of the invention is as follows:
a compound with an ethylenic bond-containing seven-membered ring as a core, wherein the structure of the compound is shown as a general formula (1):
in the general formula (1), the dotted line represents that two groups are linked or not linked by a single bond;
a. b, c and d are respectively and independently 0 or 1;
R5、R6each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, 5-30 membered heteroaryl, substituted or unsubstituted with one or more heteroatoms;
R1、R2、R3、R4each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20An alkyl group of the formula (2) or a structure of the formula (3); and at least one of the structures is represented by a general formula (2) or a general formula (3);
Y1identical or different at each occurrence and is represented by N or C-Ra(ii) a Y at the connection site1Represented as a carbon atom;
Y2identical or different at each occurrence and is represented by N or C-Rb(ii) a Y at the connection site2Represented as a carbon atom;
in the general formulae (2) and (3), Ar1、Ar2Each independently represents a single bond, substituted or unsubstituted C6-30Arylene, 5-30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
in the general formula (3), X1Represented by-O-, -S-, -C (R)14)(R15) -or-N (R)16)-；
The R is9、R10、R11Each independently represents a hydrogen atom, a structure represented by general formula (4), general formula (5) or general formula (6);
in the general formula (4), X2、X3Each independently represents a single bond, -O-, -S-, -C (R)17)(R18) -or-N (R)19) -; and X2、X3Not simultaneously represent a single bond;
Y3each occurrence being the same or different and being represented by a nitrogen atom or C-Rc；
In the general formula (5), R12、R13Each independently represents substituted or unsubstituted C6-30Aryl, 5-30 membered heteroaryl, substituted or unsubstituted with one or more heteroatoms;
in the general formula (6), Y4Each occurrence being the same or different and being represented by a nitrogen atom or C-Rd；
The R isa、Rb、Rc、RdEach independently represents a hydrogen atom, protium, deuterium, tritium, halogen atom, cyano group, C1-20Straight chain alkyl, C3-20Branched alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the R is14～R19Each independently represents C1-20Alkyl, substituted or unsubstituted C6-30Aryl, 5-30 membered heteroaryl, substituted or unsubstituted with one or more heteroatoms; and R is14And R15、R17And R18Can be bonded to each other to form a ring;
the two adjacent positions marked by the symbols in the general formula (4) and the general formula (6) are connected with the two adjacent positions marked by the symbols in the general formula (2) or the general formula (3) in a ring-by-ring mode;
Y1、Y2、Y3and Y4At least one of which is represented by N;
the substituent of the substitutable group is selected from protium, deuterium, tritium, cyano, halogen atom, C1-20Alkyl of (C)6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, Ar is1、Ar2Represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted naphthyridinyl group, or a substituted or unsubstituted pyridinylene group;
the R isa、Rb、Rc、RdEach independently represents one of hydrogen atom, protium, deuterium, tritium, fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl and substituted or unsubstituted 9, 9-spirofluorenyl;
the R is12、R13Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl, substituted or unsubstituted 9, 9-spirofluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted phenanthryl and substituted or unsubstituted anthryl;
the R is14～R19Each independently represents one of methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted pyridyl;
the substituent of the substitutable group is selected from one or more of fluorine atom, cyano-group, phenyl group, biphenyl group, naphthyl group, furyl group, carbazolyl group, thienyl group or pyridyl group.
As a further development of the invention, when the dotted line indicates that two radicals are linked by a single bond, Y is1、Y2、Y3And Y4Wherein only one is represented by N and the others are represented by carbon atoms, R9、R10And only one is represented as a hydrogen atom.
As a further development of the invention, when the dotted line indicates that the two radicals are not connected, Y is1、Y2、Y3And Y4Wherein only one is represented by N and the others are represented by carbon atoms, R9、R10And only one is represented as a hydrogen atom.
As a further development of the invention, when the dotted line indicates that two radicals are linked by a single bond, Y is1、Y2、Y3And Y4Wherein only one is represented by N and at least one is represented by RaOr RbNot being represented by a hydrogen atom, R9、R10Are all represented as hydrogen atoms. The compound taking the seven-membered ring containing the olefinic bond as the core has the specific structure as follows:
An organic electroluminescent device having a plurality of organic thin film layers between an anode and a cathode, wherein at least one of the organic thin film layers contains the compound having an ethylenic bond-containing seven-membered ring as a core.
An organic electroluminescent device, wherein an electron blocking material or a hole transporting material of the organic electroluminescent device contains the compound having the ethylenic bond seven-membered ring as a core.
An organic electroluminescent device, wherein a luminescent layer material of the organic electroluminescent device contains the compound taking the ethylenic bond-containing seven-membered ring as a core.
A display element comprising the organic electroluminescent device.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the compound of the invention takes an ethylenic bond-containing seven-membered ring as a core, is connected with an electron-donating group, has high triplet state energy level (T1), can effectively block exciton energy of a luminescent layer from being transferred to a hole transport layer when being used as an electron blocking layer material of an OLED luminescent device, improves the recombination efficiency of excitons in the luminescent layer, improves the energy utilization rate, and thus improves the luminescent efficiency of the device.
(2) The compound of the invention ensures that the distribution of electrons and holes in the luminescent layer is more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; the exciton utilization rate and the high fluorescence radiation efficiency can be effectively improved, the voltage of the device is reduced, the current efficiency of the device is improved, and the service life of the device is prolonged; thereby making it easier to obtain high efficiency of the device. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
in the figure, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a first hole transport layer, 5 is a second hole transport layer, 6 is a light emitting layer, 7 is an electron transport layer, 8 is an electron injection layer, and 9 is a cathode reflective electrode layer.
Fig. 2 is a graph of the current efficiency of the device of the present invention as a function of temperature.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
All the raw materials in the following examples were purchased from Zhongxiao Wangrun Fine chemical industries, Ltd.
Example 1: preparation of intermediate M:
starting material B-1(0.5mmol) was dissolved in tetrahydrofuran (1.5ml) and the solution was cooled to-78 deg.C (dry ice/acetone). The mixture was then treated with a small amount of trimethylsilyldiazomethane (2M, 0.25ml, 0.5mmol) in ether until the intense color of starting material B-1 disappeared; the mixture was allowed to slowly warm to-45 ℃ until N was observed2Elimination of (2). Then, the starting material A-1(0.5mmol) was added, and the mixture was left for 10 minutes in an ice bath (0 ℃ C.), and a solution of tetrabutylammonium fluoride (1M in tetrahydrofuran, 1ml, 1mmol) was added to the solution. After removal of the solvent under vacuum, the crude product was purified by column chromatography to afford intermediate M-1. Elemental analysis Structure (molecular formula C)28H17Br): theoretical value C, 77.61; h, 3.95; br, 18.44; test values are: c, 77.62; h, 3.95; br,18.43. ESI-MS (M/z) (M +): theoretical value is 432.05, found 432.51.
The intermediate M is prepared by a synthesis method of the intermediate M-1, and the specific structure is shown in Table 1.
TABLE 1
Example 2: synthesis of Compound 3:
0.01mol of intermediate M-1 and 0.012mol of starting material C-1 were dissolved in 150mL of a mixed solution of toluene and ethanol (V toluene: V ethanol ═ 5: 1), deoxygenated, and then 0.0002mol of Pd (PPh) was added3)4And 0.02mol of K2CO3Reacting at 110 ℃ for 24 hours in the atmosphere of introducing nitrogen, sampling a sample, cooling and filtering after the raw materials react completely, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a compound 3; elemental analysis Structure (molecular formula C)51H30N2O): theoretical value C, 89.19; h, 4.40; n, 4.08; test values are: c, 89.19; h, 4.40; and N, 4.07. ESI-MS (M/z) (M +): theoretical value is 686.24, found 686.54.
Example 3: synthesis of compound 12:
compound 12 is prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-2 and starting material C-1 is replaced with starting material C-2; elemental analysis Structure (molecular formula C)51H30N2O): theoretical value C, 89.19; h, 4.40; n, 4.08; test values are: c, 89.19; h, 4.40; and N, 4.07. ESI-MS (M/z) (M +): theoretical value of 686.24, found value of 686.79。
Example 4: synthesis of compound 19:
compound 19 was prepared as in example 2, except that the starting material C-1 was replaced with the starting material C-3; elemental analysis Structure (molecular formula C)54H36N2): theoretical value C, 90.98; h, 5.09; n, 3.93; test values are: c, 90.97; h, 5.09; and N, 3.94. ESI-MS (M/z) (M +): theoretical value is 712.29, found 712.92.
Example 5: synthesis of compound 30:
a250 ml three-necked flask was charged with 0.01mol of the starting D-1, 0.012mol of the intermediate M-2, 0.03mol of potassium tert-butoxide, 1 × 10 in a nitrogen-purged atmosphere-4molPd2(dba)3，1×10-4Heating and refluxing triphenylphosphine and 150ml toluene for 12 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain a compound 30; elemental analysis Structure (molecular formula C)48H32N2): theoretical value C, 90.54; h, 5.07; n, 4.40; test values are: c, 90.53; h, 5.07; and N, 4.40. ESI-MS (M/z) (M +): theoretical value is 636.26, found 636.78.
Example 6: synthesis of compound 41:
compound 41 is prepared as in example 2, except that intermediate M-3 is substituted for intermediate M-1 and starting material C-4 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)57H35N3): theoretical value C, 89.85; h, 4.63; n, 5.52; test values are: c, 89.84; h, 4.63; n, 5.53. ESI-MS (M/z) (M +): theoretical value is 761.28, found 761.86.
Example 7: synthesis of compound 52:
compound 52 is prepared as in example 2, except that intermediate M-4 is substituted for intermediate M-1 and starting material C-5 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)51H32N2O): theoretical value C, 88.93; h, 4.68; n, 4.07; test values are: c, 88.93; h, 4.68; and N, 4.06. ESI-MS (M/z) (M +): theoretical value is 688.25, found 688.84.
Example 8: synthesis of compound 61:
compound 61 can be prepared as in example 2, except that intermediate M-5 is substituted for intermediate M-1 and starting material C-6 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)51H32N2O2): theoretical value C, 86.91; h, 4.58; n, 3.97; test values are: c, 86.91; h, 4.58; and N, 3.96. ESI-MS (M/z) (M +): theoretical value is 704.25, found 704.74.
Example 9: synthesis of compound 71:
compound 71 is prepared as in example 2, except that intermediate M-6 is substituted for intermediate M-1 and starting material C-7 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)54H38N2): theoretical value C, 90.72; h, 5.36; n, 3.92; test values are: c, 90.71; h, 5.36; and N, 3.93. ESI-MS (M/z) (M +): theoretical value is 714.30, found 714.88.
Example 10: synthesis of compound 86:
compound 86 is prepared as in example 2, except that intermediate M-6 is substituted for intermediate M-1 and starting material C-8 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)57H37N3): theoretical value C, 89.62; h, 4.88; n, 5.50; test values are: c, 89.61; h, 4.88; n, 5.51. ESI-MS (M/z) (M +): the theoretical value is 763.30, found 763.74.
Example 11: synthesis of compound 94:
compound 94 was prepared as in example 2, except that the starting material C-1 was replaced with the starting material C-9; elemental analysis Structure (molecular formula C)57H37N3): theoretical value C, 89.62; h, 4.88; n, 5.50; test values are: c, 89.61; h, 4.88; n, 5.51. ESI-MS (M/z) (M +): theoretical value is 763.30, found 763.44.
Example 12: synthesis of compound 108:
compound 108 is prepared as in example 2, except that intermediate M-7 is substituted for intermediate M-1 and starting material C-10 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)55H34N2): theoretical value C, 91.38; h, 4.74; n, 3.88; test values are: c, 91.37; h, 4.74; and N, 3.89. ESI-MS (M/z) (M +): theoretical value is 722.27, found 722.45.
Example 13: synthesis of compound 119:
compound 119 can be prepared as in example 5, except that intermediate M-7 is substituted for intermediate M-1 and starting material D-2 is substituted for starting material D-1; elemental analysis Structure (molecular formula C)43H26N2): theoretical value C, 90.50; h, 4.59; n, 4.91; test values are: c, 90.51; h, 4.59; and N, 4.90. ESI-MS (M/z) (M +): theoretical value is 570.21, found 570.77.
Example 14: synthesis of compound 130:
compound 130 is prepared as in example 2, except that intermediate M-8 is substituted for intermediate M-1 and starting material C-11 is substituted for starting material C-1; elemental analysis Structure (molecular formula C)51H32N2O): theoretical value C, 88.93; h, 4.68; n, 4.07; test values are: c, 88.93; h, 4.68; and N, 4.08. ESI-MS (M/z) (M +): theoretical value is 688.25, found 688.84.
Example 15: synthesis of compound 142:
compound 142 is prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-5 and starting material C-1 is replaced with starting material C-12; elemental analysis Structure (molecular formula C)54H38N2): theoretical value C, 90.72; h, 5.36; n, 3.92; test values are: c, 90.73; h, 5.36; and N, 3.91. ESI-MS (M/z) (M +): theoretical value is 714.30, found 714.84.
Example 16: synthesis of compound 149:
compound 149 is prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-9 and starting material C-1 is replaced with starting material C-13; elemental analysis Structure (molecular formula C)60H42N2): theoretical value C, 91.11; h, 5.35; n, 3.54; test values are: c, 91.10; h, 5.35; and N, 3.55. ESI-MS (M/z) (M +): theoretical value is 790.33, found 790.76.
Example 17: synthesis of compound 162:
compound 162 is prepared as in example 2, except that intermediate M-1 is replaced with intermediate M-2 and starting material C-1 is replaced with starting material C-14; elemental analysis Structure (molecular formula C)63H41N3): theoretical value C, 90.08; h, 4.92; n, 5.00; test values are: c, 90.07; h, 4.92; and N, 5.01. ESI-MS (M/z) (M +): theoretical value is 839.33, found 839.63.
The organic compound of the present invention is used in a light-emitting device, and can be used as a hole transport layer material. The T1 energy level, thermal property and HOMO energy level were measured for compounds 3, 12, 19, 30, 41, 52, 61, 71, 86, 94, 108, 119, 130, 142, 149, 162, 173, 179, 180 and 182 of the present invention, respectively, and the results are shown in table 2.
TABLE 2
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of (4); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy testing system (IPS3) in an atmospheric environment.
As can be seen from the data in table 2 above, the organic compound of the present invention has a suitable HOMO energy level, and can be applied to a hole transport layer or a light emitting layer, and the organic compound of the present invention having an ethylenic linkage seven-membered ring as a core has a higher triplet energy level and a higher thermal stability, so that the efficiency and the lifetime of the OLED device containing the organic compound of the present invention are both improved.
The effect of the application of the synthesized compound of the present invention in the device is explained in detail by device examples 1 to 21 and device comparative example 1 below. Device examples 2 to 21 and device comparative example 1 compared with device example 1, the manufacturing processes of the devices were completely the same, and the same substrate material and electrode material were used, and the film thicknesses of the electrode materials were also kept the same, except that the hole transport layer or the light emitting layer material was changed in the devices. The device stack structure is shown in table 3, and the performance test results of each device are shown in tables 4 and 5.
Device example 1
As shown in fig. 1, a method for manufacturing an electroluminescent device includes the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;
b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3;
c) evaporating a hole transport material HT-1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material HT-1 is 60nm, and the hole transport material HT-1 is a first hole transport layer 4;
d) a second hole transport layer material, namely a compound 3 prepared in the embodiment of the invention, is evaporated on the first hole transport layer 4 in a vacuum evaporation mode, the thickness of the compound is 20nm, and the layer is a second hole transport layer 5;
e) and a light-emitting layer 6 is evaporated on the second hole transport layer 5, the host materials are GH-1 and GH-2, the doping materials are GD-1, and the mass ratio of GH-1, GH-2 and GD-1 is 45: 45: 10, thickness of 40 nm;
f) evaporating electron transport materials ET-1 and Liq on the light emitting layer 6 in a vacuum evaporation mode according to the mass ratio of 1:1, wherein the thickness is 35nm, and the organic material of the layer is used as a hole blocking/electron transport layer 7;
g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8;
h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9;
after the electroluminescent device was fabricated according to the above procedure, IVL data and light decay life of the device were measured, and the results are shown in table 4. The molecular structural formula of the related material is shown as follows:
TABLE 3
The efficiency and lifetime data for each device example and device comparative example 1 are shown in table 4.
TABLE 4
Note: LT97 refers to a current density of 10mA/cm2In the case, the time taken for the luminance of the device to decay to 97%;
the life test system is a Korean pulse science M600 type OLED device life tester.
As can be seen from the device data results of table 3, the organic light emitting device of the present invention achieves a greater improvement in both efficiency and lifetime over OLED devices of known materials.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 1, 8 and 21 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 5 and the figure 2.
TABLE 5
As can be seen from the data in table 5 and fig. 2, device examples 1, 8, and 21 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A compound having an ethylenic bond-containing seven-membered ring as a core, characterized in that the structure of the compound is represented by the general formula (1):
in the general formula (1), the dotted line represents that two groups are linked or not linked by a single bond;
a. b, c and d are respectively and independently 0 or 1;
R5、R6each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20Alkyl, substituted or unsubstituted C6-30Aryl, 5-30 membered heteroaryl, substituted or unsubstituted with one or more heteroatoms;
R1、R2、R3、R4each independently represents a hydrogen atom, protium, deuterium, tritium, cyano group, halogen, C1-20An alkyl group of the formula (2) or a structure of the formula (3); and at least one of the structures is represented by a general formula (2) or a general formula (3);
Y1identical or different at each occurrence and is represented by N or C-Ra(ii) a Y at the connection site1Represented as a carbon atom;
Y2identical or different at each occurrence and is represented by N or C-Rb(ii) a Y at the connection site2Represented as a carbon atom;
in the general formulae (2) and (3), Ar1、Ar2Each independently represents a single bond, substituted or unsubstituted C6-30Arylene, 5-30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
in the general formula (3), X1Represented by-O-, -S-, -C (R)14)(R15) -or-N (R)16)-；
The R is9、R10、R11Each independently represents a hydrogen atom, a structure represented by general formula (4), general formula (5) or general formula (6);
in the general formula (4), X2、X3Each independently represents a single bond, -O-, -S-, -C (R)17)(R18) -or-N (R)19) -; and X2、X3Not simultaneously represent a single bond;
Y3each occurrence being the same or different and being represented by a nitrogen atom or C-Rc；
In the general formula (5), R12、R13Each independently represents substituted or unsubstituted C6-30Aryl radicals containing one or more5-30 membered heteroaryl substituted or unsubstituted with a heteroatom;
in the general formula (6), Y4Each occurrence being the same or different and being represented by a nitrogen atom or C-Rd；
The R isa、Rb、Rc、RdEach independently represents a hydrogen atom, protium, deuterium, tritium, halogen atom, cyano group, C1-20Straight chain alkyl, C3-20Branched alkyl, substituted or unsubstituted C6-30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the R is14～R19Each independently represents C1-20Alkyl, substituted or unsubstituted C6-30Aryl, 5-30 membered heteroaryl, substituted or unsubstituted with one or more heteroatoms; and R is14And R15、R17And R18Can be bonded to each other to form a ring;
the two adjacent positions marked by the symbols in the general formula (4) and the general formula (6) are connected with the two adjacent positions marked by the symbols in the general formula (2) or the general formula (3) in a ring-by-ring mode;
Y1、Y2、Y3and Y4At least one of which is represented by N;
the substituent of the substitutable group is selected from protium, deuterium, tritium, cyano, halogen atom, C1-20Alkyl of (C)6-30One or more of aryl, 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
2. The compound of claim 1, wherein Ar is Ar1、Ar2Represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted naphthyridinyl group, or a substituted or unsubstituted pyridinylene group;
the R isa、Rb、Rc、RdEach independently represents one of hydrogen atom, protium, deuterium, tritium, fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl and substituted or unsubstituted 9, 9-spirofluorenyl;
the R is12、R13Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl, substituted or unsubstituted 9, 9-spirofluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted phenanthryl and substituted or unsubstituted anthryl;
the R is14～R19Each independently represents one of methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted pyridyl;
the substituent of the substitutable group is selected from one or more of fluorine atom, cyano-group, phenyl group, biphenyl group, naphthyl group, furyl group, carbazolyl group, thienyl group or pyridyl group.
3. A compound according to claim 1, wherein Y is when the dotted line indicates that two groups are connected by a single bond1、Y2、Y3And Y4Wherein only one is represented by N and the others are represented byIs a carbon atom, R9、R10And only one is represented as a hydrogen atom.
4. A compound according to claim 1, wherein Y is when the dotted line indicates that the two groups are not connected1、Y2、Y3And Y4Wherein only one is represented by N and the others are represented by carbon atoms, R9、R10And only one is represented as a hydrogen atom.
5. A compound according to claim 1, wherein Y is when the dotted line indicates that two groups are connected by a single bond1、Y2、Y3And Y4Wherein only one is represented by N and at least one is represented by RaOr RbNot being represented by a hydrogen atom, R9、R10Are all represented as hydrogen atoms.
6. The compound of claim 1, wherein the specific structure of the compound having an ethylenic seven-membered ring as a core is:
7. An organic electroluminescent device comprising a plurality of organic thin film layers between an anode and a cathode, wherein at least one of the organic thin film layers comprises the compound having an ethylenic seven-membered ring as a core according to any one of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, wherein the electron blocking material or the hole transporting material of the organic electroluminescent device comprises the compound having an ethylenic seven-membered ring as a core according to any one of claims 1 to 6.
9. The organic electroluminescent device according to claim 7, wherein the material of the light-emitting layer of the organic electroluminescent device comprises the compound having an ethylenic seven-membered ring as a core according to any one of claims 1 to 6.
10. A display element comprising the organic electroluminescent device according to any one of claims 7 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811593762.1A CN111362936A (en) | 2018-12-25 | 2018-12-25 | Compound with olefinic bond-containing seven-membered ring as core and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811593762.1A CN111362936A (en) | 2018-12-25 | 2018-12-25 | Compound with olefinic bond-containing seven-membered ring as core and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111362936A true CN111362936A (en) | 2020-07-03 |
Family
ID=71203957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811593762.1A Pending CN111362936A (en) | 2018-12-25 | 2018-12-25 | Compound with olefinic bond-containing seven-membered ring as core and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111362936A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651364A (en) * | 2019-01-29 | 2019-04-19 | 北京诚志永华显示科技有限公司 | New compound, electroluminescent organic material, organic electroluminescence device, electronic equipment |
| CN110835305A (en) * | 2018-08-17 | 2020-02-25 | 江苏三月光电科技有限公司 | Organic compound containing dibenzosuberene, preparation method and application thereof |
| CN112239452A (en) * | 2020-10-14 | 2021-01-19 | 武汉尚赛光电科技有限公司 | Electron transport type heteroanthracene derivative and organic electroluminescent device thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468245A (en) * | 2013-08-16 | 2013-12-25 | 石家庄诚志永华显示材料有限公司 | OLED material with carrier transmittability as well as preparation method and application thereof |
-
2018
- 2018-12-25 CN CN201811593762.1A patent/CN111362936A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468245A (en) * | 2013-08-16 | 2013-12-25 | 石家庄诚志永华显示材料有限公司 | OLED material with carrier transmittability as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| MORDECAI RABINOVITZ ET AL.: "Fulvenes and Thermochromic Ethylenes. Part XL1V.l Shielding Effects in Diphenylmethylenef luorene, Fluorenylidenetriphenylphosphorane, and Related Substances", 《J. CHEM. SOC. (B)》 * |
| RADICAL ANIONS ET AL.: "EPR，ENDOR and TRIPLE Resonance Characterization of Three Paramagnetic Reduction Stages of 5-(9"=Fluorenylidene)-5H=dibenzo [a,d] cycloheptene", 《J. CHEM. SOC. FARADAY TRANS.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835305A (en) * | 2018-08-17 | 2020-02-25 | 江苏三月光电科技有限公司 | Organic compound containing dibenzosuberene, preparation method and application thereof |
| CN110835305B (en) * | 2018-08-17 | 2022-12-02 | 江苏三月科技股份有限公司 | Organic compound containing dibenzosuberene, preparation method and application thereof |
| CN109651364A (en) * | 2019-01-29 | 2019-04-19 | 北京诚志永华显示科技有限公司 | New compound, electroluminescent organic material, organic electroluminescence device, electronic equipment |
| CN112239452A (en) * | 2020-10-14 | 2021-01-19 | 武汉尚赛光电科技有限公司 | Electron transport type heteroanthracene derivative and organic electroluminescent device thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110577510B (en) | Compound based on bis-dimethyl fluorene substituted aniline and organic electroluminescent device prepared from compound | |
| CN109836339B (en) | Triarylamine organic compound and application thereof | |
| CN109912431B (en) | Triarylamine organic compound containing naphthalene and application thereof | |
| CN111662258A (en) | Organic compound containing pyrene and application thereof in OLED | |
| CN111662259A (en) | Organic compound containing pyrene and application thereof in organic electroluminescent device | |
| CN111662187A (en) | Amino-containing organic compound and application thereof | |
| CN110885334A (en) | Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof | |
| CN111662190A (en) | Organic compound containing pyrene or aza-pyrene and application thereof | |
| CN111943941A (en) | Compound with xanthone as core and application thereof | |
| CN112479903B (en) | Organic compound with mesitylene as core and application thereof | |
| CN111362936A (en) | Compound with olefinic bond-containing seven-membered ring as core and application thereof | |
| CN111943857B (en) | Triarylamine organic compound and application thereof | |
| CN113135903A (en) | Aromatic dibenzofuran derivative and application thereof | |
| CN110642732B (en) | Organic compound containing spirofluorene anthrone structure and application thereof | |
| CN112479978A (en) | Organic compound with carbazole derivative as core and application thereof | |
| CN110577523B (en) | Compound containing triarylamine structure and organic electroluminescent device prepared from compound | |
| CN110577508B (en) | Compound with triarylamine as core and application thereof | |
| CN110963904A (en) | Compound with ketone and fluorene as cores, preparation method and application thereof | |
| CN113121515A (en) | Compound with dibenzo five-membered heterocycle as core and application thereof | |
| CN111253410A (en) | Compound with fluorene as core and application thereof | |
| CN110734444B (en) | Compound with azaspirofluorene as core and application thereof | |
| CN111362959A (en) | Compound with olefinic bond-containing fluorene as core and application thereof | |
| CN109912592B (en) | Compound containing pyridoindole and application of compound in organic electroluminescent device | |
| CN111362955A (en) | Organic compound and application thereof to OLED device | |
| CN112479905B (en) | Organic compound containing benzoanthracene fluorene and diarylamine and application thereof in organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 214112 Wuxi New District, Jiangsu, Xinzhou Road, No. 210 Applicant after: Jiangsu March Technology Co.,Ltd. Address before: 214112 Wuxi New District, Jiangsu, Xinzhou Road, No. 210 Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200703 |
|
| RJ01 | Rejection of invention patent application after publication |